CN110869453A - Photocurable ink composition for inkjet printing - Google Patents

Photocurable ink composition for inkjet printing Download PDF

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Publication number
CN110869453A
CN110869453A CN201880046555.6A CN201880046555A CN110869453A CN 110869453 A CN110869453 A CN 110869453A CN 201880046555 A CN201880046555 A CN 201880046555A CN 110869453 A CN110869453 A CN 110869453A
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CN
China
Prior art keywords
ink composition
mass
inkjet printing
present
photocurable
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Pending
Application number
CN201880046555.6A
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Chinese (zh)
Inventor
佐藤洋一
中岛兴范
明濑拓哉
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Sakata Inx Corp
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Sakata Inx Corp
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Publication of CN110869453A publication Critical patent/CN110869453A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/26—Printing on other surfaces than ordinary paper
    • B41M1/28—Printing on other surfaces than ordinary paper on metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0023—Digital printing methods characterised by the inks used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5397—Phosphine oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

Abstract

The present invention addresses the problem of obtaining an ink composition that has sufficiently high adhesion and heat resistance to metal surfaces, as an ink composition for inkjet printing that can be used for inkjet printing, particularly on metal surfaces. The present invention provides a photocurable ink composition for inkjet printing, which is characterized by containing an acid-modified acrylic monomer in an amount of 0.1% by mass or more, a monofunctional monomer having a Tg of 100 ℃ or more in an amount of 10 to 30% by mass, and a monofunctional monomer in an amount of 80% by mass or more, based on the total amount of all the monomers.

Description

Photocurable ink composition for inkjet printing
Technical Field
The present invention relates to a photocurable ink composition for ink jet printing for metal.
Background
As described in patent documents 1 and 2, an ultraviolet-curable offset ink for inkjet containing an acid-modified acrylic monomer is known.
However, such an ink containing an acid-modified acrylic monomer may not cause any problem when used as an ink for offset printing for printing on paper, but when a printed object such as a metal sheet is made of metal, it does not have sufficient adhesion and heat resistance to the surface of the printed object.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2006-016507
Patent document 2: japanese patent laid-open publication No. 2006 + 016508
Disclosure of Invention
The present invention addresses the problem of obtaining an ink composition for inkjet printing that can be used for inkjet printing, particularly on metal surfaces, that has sufficiently high adhesion and heat resistance to metal surfaces.
The present inventors have conducted intensive studies to solve the above problems, and as a result, completed the present invention with a photocurable inkjet printing ink composition containing an acid-modified acrylic monomer and a monofunctional monomer having a Tg (glass transition temperature) of 100 ℃.
Namely, the present invention is that,
1. a photocurable ink composition for inkjet printing, characterized in that, with respect to the entire ink composition,
containing an acid-modified acrylic monomer in an amount of 0.1% by mass or more,
10 to 30 mass% of a monofunctional monomer having a Tg of 100 ℃ or higher,
with respect to all of the monomers, the monomer,
the monomer contains a monofunctional monomer in an amount of 80% by mass or more.
2. The photocurable inkjet printing ink composition according to claim 1, wherein the monofunctional monomer having a Tg of 100 ℃ or higher is a monofunctional monomer having a Tg of 120 ℃ or higher.
The present invention is an invention that can exhibit a remarkable effect of sufficiently having high adhesion and heat resistance particularly to a metal surface.
Detailed Description
The photocurable inkjet printing ink composition of the present invention (hereinafter also referred to as the ink composition of the present invention) will be described in detail below.
< acid-modified acrylic acid monomer >
The acid-modified acrylic monomer of the present invention is a monomer component obtained by esterification of a polymer of a polyhydric alcohol and (meth) acrylic acid and/or (meth) acrylic acid with 1 or more kinds of condensation products of phosphoric acid, C3-20 fatty acids, and C3-20 fatty acids and (meth) acrylic acid, and has an acid value of 100mgKOH/g or more when the acid-modified acrylic monomer is a homopolymer.
Specifically, an acid-modified acrylic monomer having a structure in which a part of hydroxyl groups of a polyol are ester-bonded to (meth) acrylic acid and the other hydroxyl groups are ester-bonded to phosphoric acid is preferable.
In the present invention, the photocurable inkjet printing ink composition contains 0.1% by mass or more of an acid-modified acrylic monomer, preferably 0.3 to 3.0% by mass of an acid-modified acrylic monomer, and more preferably 0.4 to 1.5% by mass of an acid-modified acrylic monomer. When the content is less than 0.1% by mass, adhesion to aluminum is poor, and filterability immediately after production and after long-term storage of the ink composition is poor.
< monofunctional monomer having Tg of 100 ℃ or higher >
Examples of the monofunctional monomer having a Tg of 100 ℃ or higher in the present invention include Acryloylmorpholine (ACMO) (145 ℃), N-Vinylcaprolactam (VCAP) (125 ℃), methyl Methacrylate (105 ℃), acrylamide (165 ℃), acrylic acid (106 ℃), dicyclopentyl Methacrylate (175 ℃), dicyclopentyl acrylate (120 ℃), isobornyl Methacrylate (173 ℃), and 1-Adamantyl Methacrylate (1-Adamantyl Methacrylate) (153 ℃). Among them, Tg of 120 ℃ or higher is preferable.
The monofunctional monomer having a Tg of 100 ℃ or higher means that the Tg of the monofunctional monomer as a homopolymer is 100 ℃ or higher.
The content of the monofunctional monomer is 10 to 30% by mass, preferably 15 to 25% by mass, based on the entire ink composition. When the amount is less than 10% by mass, the heat resistance of the coating film is deteriorated, and when it exceeds 30% by mass, the adhesion to aluminum is deteriorated.
< monofunctional monomer >
The monofunctional monomer of the present invention is not particularly limited as long as it has a Tg of 100 ℃ or higher, examples thereof include ethylcarbitol acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylonitrile, methylstyrene, cyclohexyl methacrylate, vinyl acetate, N-propyl methacrylate, N-butyl methacrylate, methyl acrylate, 2-hydroxy-3-phenoxypropyl 2-acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, N- [3- (Dimethylamino) propyl ] acrylamide and N- [3- (Dimethylamino) propyl ] methacrylamide.
The content of the monofunctional monomer in the ink composition of the present invention is 80% by mass or more, preferably 85% by mass or more, of all the monomers.
< extender pigment >
Extender pigments can be formulated in the present invention. Examples of such extender pigments include silica, alumina and calcium carbonate.
When such an extender pigment is blended, the content of the extender pigment in the ink composition is 0.1% by mass or more, preferably 0.5 to 7.0% by mass, and more preferably 0.7 to 5.0% by mass.
< polyfunctional monomer and photopolymerizable oligomer >
In the present invention, the following polyfunctional monomers, photopolymerizable oligomers or polymers may be used in combination as the other photopolymerizable components within the range not to impair the effects of the present invention.
As such another photopolymerizable component, a monomer, a prepolymer, an oligomer, or the like can be used without particular limitation as long as it is a compound containing an ethylenic double bond.
Examples of such photopolymerizable components include amino-modified acrylic oligomers, ethyleneoxyethoxy (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, 1, 6-hexanediol diacrylate (HDDA), dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate and other (poly) alkylene glycol di (meth) acrylates, trimethylolpropane tri (meth) acrylate and its ethylene oxide-modified product, pentaerythritol tetra (meth) acrylate and its ethylene oxide-modified product, dipentaerythritol penta (meth) acrylate and its ethylene oxide-modified product, and mixtures thereof, Examples of the other photopolymerizable components include dipentaerythritol hexa (meth) acrylate and ethylene oxide-modified products thereof, (meth) acrylic acid urethane, epoxy (meth) acrylate, and polyester (meth) acrylate, and examples of the amino group-containing polyfunctional monomer include CN371, CN550, and CN551 manufactured by Sartomer corporation, AgiSyn001, AgiSyn002, AgiSyn003, AgiSyn005, AgiSyn006, AgiSyn007, and AgiSyn008 manufactured by DSM-Agi corporation, and EBECRYL80 and EBECRYL7100 (both trade names) manufactured by Daicel-allnex corporation. Of these, 1 or more may be used as needed.
Among them, amino-modified acrylic oligomers are preferably used.
< non-polymerizable resin >
Further, as the non-polymerizable resin, an amine-modified acrylate oligomer (trade name: CN371NS, manufactured by Sartomer Co.) or an aromatic ketone-formaldehyde condensation type hydrogen addition ketone resin may be used in combination. 1 or more, if necessary, 2 or more of the other photopolymerizable components or non-polymerizable resins described above may be used.
< photopolymerization initiator >
The photocurable inkjet printing ink composition of the present invention contains a photopolymerization initiator.
As the photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator (compound) or a thioxanthone-based photopolymerization initiator (compound) which exhibits an initiator function by light having a wavelength of 300 to 450nm is preferable. The above-mentioned "the initiator function is exhibited by light having a wavelength of 300 to 450 nm" means that the whole wavelength region of 300 to 450nm has a light absorption property. By using such an acylphosphine oxide-based photopolymerization initiator or a thioxanthone-based photopolymerization initiator, the photocurable inkjet printing ink composition of the present invention can be further provided with curability with respect to an LED.
Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name: TPO, manufactured by Lambson), bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide (trade name: IRGACURE 819, manufactured by BASF), and the like.
Specific examples of the thioxanthone photopolymerization initiator include 2, 4-Diethylthioxanthone (DETX), 2-isopropylthioxanthone, and 4-isopropylthioxanthone.
The content of the acylphosphine oxide-based photopolymerization initiator or the thioxanthone-based photopolymerization initiator is preferably 3 to 25% by mass, more preferably 5 to 15% by mass, based on the total mass of the photopolymerizable components. If the content of the acylphosphine oxide-based photopolymerization initiator or the thioxanthone-based photopolymerization initiator is less than 3% by mass, curability may be insufficient. On the other hand, if it exceeds 25 mass%, the storage stability of the photocurable inkjet printing ink composition of the present invention is lowered.
< sensitizing agent >
In order to further promote the curing with respect to ultraviolet rays, a photosensitizer (compound) having light absorption characteristics mainly in the wavelength region of ultraviolet rays of 400nm or more and exhibiting a sensitizing function of a curing reaction by light of a wavelength in this range may be used in combination in the photocurable inkjet printing ink composition of the present invention.
The above-mentioned "the sensitizing function is exhibited by light having a wavelength of 400nm or more" means that the light-absorbing property is exhibited in a wavelength region of 400nm or more. By using such a sensitizer, the LED curability of the photocurable inkjet printing ink composition of the present invention can be promoted.
The photosensitizer is an anthracene sensitizer, a thioxanthone sensitizer, or the like, and a thioxanthone sensitizer is preferable. These can be used alone or in combination of 2 or more.
Specific examples thereof include anthracene-based sensitizers such as 9, 10-dibutoxyanthracene, 9, 10-diethoxyanthracene, 9, 10-dipropoxyanthracene, and 9, 10-bis (2-ethylhexyloxy) anthracene, and thioxanthone-based sensitizers such as 2, 4-diethylthioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone. Typical examples of commercially available sensitizers include DBA and DEA (manufactured by kawasaki chemical industry), and examples of thioxanthone sensitizers include DETX and ITX (manufactured by Lambson).
The content of the sensitizer is preferably in the range of 0 to 8% by mass relative to the total mass of the photopolymerizable components. When the amount exceeds 8 mass%, the effect is not improved and the amount is excessively added, which is not preferable.
< coloring agent >
The photocurable inkjet printing ink composition of the present invention may further contain a colorant of each hue to obtain a photocurable inkjet printing ink composition of each color. In some cases, even when the primer was colored, the presence or absence of the formation of the primer layer could be confirmed.
As such a colorant, pigments and dyes conventionally used in photocurable inkjet printing ink compositions can be used without particular limitation, but in view of light resistance, pigments such as organic pigments and inorganic pigments are preferable.
Examples of the organic coloring pigment include dye lake pigments, azo pigments, benzimidazolone pigments, phthalocyanine pigments, quinacridone pigments, Anthraquinone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, isoindolinone pigments, nitro pigments, nitroso pigments, Anthraquinone pigments, xanthenone pigments, quinophthalone pigments, pyranthrone pigments, indanthrone pigments, and the like. Examples of the inorganic coloring pigment include carbon black, titanium oxide, red iron oxide, graphite, iron black, and green chromium oxide.
Specific examples of pigments having typical hues of the photocurable ink composition for inkjet printing according to the present invention include the following pigments.
First, examples of the Yellow Pigment used as the photocurable Yellow ink composition for inkjet printing include c.i. Pigment Yellow (Pigment Yellow)1, 2, 3, 12, 13, 14, 16, 17, 42, 73, 74, 75, 81, 83, 87, 93, 95, 97, 98, 108, 109, 114, 120, 128, 129, 138, 139, 150, 151, 155, 166, 180, 184, 185, 213, and the like, and c.i. Pigment Yellow 150, 155, 180, 213 and the like are preferable.
Examples of the magenta pigment used in the photocurable magenta ink composition for inkjet printing include c.i. pigment red 5, 7, 12, 22, 38, 48:1, 48:2, 48:4, 49:1, 53:1, 57:1, 63:1, 101, 102, 112, 122, 123, 144, 146, 149, 168, 177, 178, 179, 180, 184, 185, 190, 202, 209, 224, 242, 254, 255, 270, and c.i. pigment violet 19, and c.i. pigment red 122, 202, and c.i. pigment violet 19 are preferable.
Examples of the cyan pigment used in the photocurable cyan ink composition for inkjet printing include c.i. pigment blue 1, 2, 3, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 22, 27, 29, and 60, and preferably c.i. pigment blue 15: 4.
Examples of the black pigment used as the photocurable black ink composition for inkjet printing include carbon black (c.i. pigment black 7) and the like.
Examples of the white pigment used as the photocurable white ink composition for inkjet printing include titanium oxide, aluminum oxide, and the like, and titanium oxide surface-treated with various materials such as aluminum oxide, silicon dioxide, and the like is preferable.
The content of the colorant in the photocurable inkjet printing ink composition of the present invention is preferably 1 to 20% by mass based on the total amount of the photocurable inkjet printing ink composition. If the content of the colorant is less than 1 mass%, the image quality of the obtained printed matter tends to be lowered. On the other hand, if the content of the pigment exceeds 20 mass%, the viscosity characteristics of the photocurable inkjet printing ink composition tend to be adversely affected.
< inorganic particle dispersant >
The photocurable inkjet printing ink composition of the present invention may further contain an inorganic particle dispersant, which is a dispersant for inorganic particles, as necessary.
Since the inorganic particle dispersant is used to improve the dispersibility of the inorganic particles and the storage stability of the ink composition of the present invention, a dispersant conventionally used as a pigment dispersant can be used without particular limitation, but among them, a polymer dispersant is preferably used. Examples of such inorganic particle dispersants include carbodiimide dispersants, polyester amine dispersants, fatty acid amine dispersants, modified polyacrylate dispersants, modified polyurethane dispersants, multi-chain polymer nonionic dispersants, and polymer ionic activators. These inorganic particle dispersants may be used alone or in combination of 2 or more.
The inorganic particle dispersant is preferably contained in an amount of 1 to 200 parts by mass based on 100 parts by mass of the total amount of the pigment used. If the content of the inorganic particle dispersant is less than 1 part by mass, the dispersibility of the inorganic particles may be lowered, and the storage stability of the ink composition of the present invention may be lowered. On the other hand, the inorganic particle dispersant may be contained in an amount exceeding 200 parts by mass, but the effect may not be different. A more preferable lower limit of the content of the inorganic particle dispersant is 5 parts by mass, and a more preferable upper limit is 60 parts by mass.
< surfactant >
In order to improve the ejection stability, the photocurable inkjet printing ink composition of the present invention preferably contains a surfactant such as a silicon-based surfactant, which has been conventionally used as a surfactant in photocurable inkjet printing ink compositions, depending on the inkjet head to be used.
Specific examples of the silicone surfactant include polyether-modified silicone oil, polyester-modified polydimethylsiloxane, and polyester-modified methylalkylpolysiloxane (product name: BYK-315N, BYK-Chemie). These may be used alone or in combination of 2 or more.
The content of the surfactant in the ink composition of the present invention is preferably 0.005 to 1.0% by mass. When the amount is less than 0.005% by mass, the surface tension of the photocurable inkjet printing ink composition of the present invention increases, and the ejection stability from the inkjet head decreases. On the other hand, if it exceeds 1.0 mass%, the number of bubbles in the photocurable ink composition for inkjet printing increases, and the ejection stability decreases.
< additive >
In order to realize various functionalities, various additives may be added to the photocurable inkjet printing ink composition of the present invention as needed. Specifically, there may be mentioned a light stabilizer, a surface treatment agent, an antioxidant, an antiaging agent, a crosslinking accelerator, a quinone polymerization inhibitor, a plasticizer such as dioctyl maleate, a preservative, a pH adjuster, an antifoaming agent, a humectant and the like.
The photocurable ink composition for inkjet printing of the present invention may contain a solvent, but is preferably solvent-free, and the viscosity at 25 ℃ in the absence of a solvent is preferably 100cps or less, more preferably 20cps or less, and still more preferably 10cps or less. Further, the specific viscosity of the photocurable inkjet printing ink composition can be designed to be suitable for each inkjet device.
In the present specification, the viscosity refers to a viscosity measured under a measurement condition of 25 ℃ and 5 to 100rpm using a viscometer (trade name: RE215L type viscometer, manufactured by Toyobo industries Co., Ltd.).
The photocurable ink composition for inkjet printing according to the present invention can be used to form an ink composition which is excellent in curability with respect to ultraviolet rays, particularly ultraviolet rays using a Light Emitting Diode (LED) as a light source, has good adhesion to a substrate or a metal made of a polyolefin material such as polypropylene, is excellent in ejection stability and storage stability, and is excellent in all safety aspects such as a high flash point, low skin irritation, and low odor by containing the specific photopolymerizable component and the acylphosphine oxide photopolymerization initiator or the thioxanthone photopolymerization initiator in specific amounts.
The method for preparing the ink composition of the present invention is not particularly limited, and the ink composition can be prepared by adding all the above materials and mixing them by a bead mill, a three-roll mill, or the like.
Alternatively, the ink composition may be prepared by mixing a pigment, a pigment dispersant and a photopolymerizable component to obtain a concentrated base ink (concentrated base ink) composition in advance, and adding an additive such as a photopolymerizable component, a photopolymerization initiator and, if necessary, a surfactant to the concentrated base ink composition so as to obtain a desired composition of the photocurable inkjet printing ink composition.
Specifically, the method of using the ink composition of the present invention includes a method of ejecting the ink composition of the present invention onto a metal substrate (hereinafter simply referred to as "substrate") through an inkjet head, and then exposing a coating film of the ink composition of the present invention attached to the substrate to light to cure the coating film.
For example, ejection to the base material (printing of an image) can be performed by: the ink composition of the present invention is supplied to a printer head having a low viscosity corresponding to a printer for ink jet recording, and is discharged from the printer head so that the film thickness of the coating film is, for example, 1 to 60 μm with respect to the base material. The exposure and curing by light (curing of an image) can be performed by irradiating a coating film of the ink composition of the present invention applied as an image to a substrate with light.
As a printing apparatus for inkjet recording for printing the ink composition of the present invention, a conventionally used printing apparatus for inkjet recording can be used. In the case of using a continuous (continuous type) ink jet recording printing apparatus, the conductivity may be adjusted by further adding a conductivity-imparting agent to the ink composition of the present invention.
Examples of the light source for curing the coating film include ultraviolet rays (UV), ultraviolet rays (light emitting diode (LED)), electron beams, visible light, and the like, and from the environmental viewpoint, a Light Emitting Diode (LED) that generates ultraviolet rays having an emission peak wavelength in the range of 350 to 420nm is preferable.
The photocurable ink composition for inkjet printing according to the present invention can form a layer for printing certain information or the like by printing and photocuring on the surface of a substrate, and since the surface of the cured layer is excellent in adhesion to a general ink composition, a primer layer in printing with a general ink can be formed on the surface of a metal molded body.
When the ink composition of the present invention is used to form a primer layer, any general ink composition containing a photocurable or non-photocurable ink composition can be selected as the ink layer formed thereon.
Examples
Examples 1 to 5 and comparative examples 1 to 4
Preparation of photo-curable ink composition for inkjet printing
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples. In addition, "%" means "% by mass" and "part(s)" means "part(s) by mass" unless otherwise specified.
The materials used in the following examples and comparative examples are as follows.
Alumina: a dispersion (average particle diameter 80nm) was prepared by mixing 10 parts of AEROXIDE ALU-C (manufactured by AEROSIL Co., Ltd., Japan), 1 part of AJISPER PB821 (manufactured by Ajine-Techno Co., Ltd.), and 89 parts of benzyl acrylate, and dispersing the mixture with 0.2mm zirconia beads and a bead mill
CN371 NS: amine-modified acrylate oligomer (polyfunctional monomer having amino group) (manufactured by Sartomer Co., Ltd.)
SR 454: ethoxylated trimethylolpropane triacrylate (manufactured by Sartomer Co., Ltd.)
CD 9050: an acid-modified acrylic monomer having a structure in which a part of the hydroxyl groups of a polyol are ester-bonded to (meth) acrylic acid and the other hydroxyl groups are ester-bonded to phosphoric acid (manufactured by Sartomer Co., Ltd.)
CD 9051: an acid-modified acrylic monomer having a structure in which a part of the hydroxyl groups of a polyol are ester-bonded to (meth) acrylic acid and the other hydroxyl groups are ester-bonded to phosphoric acid (manufactured by Sartomer Co., Ltd.)
An SK resin: 40% by mass of solid content obtained by diluting Variplus SK (aromatic ketone-formaldehyde condensation type hydrogen-added ketone resin, Tego Co., Ltd.) with benzyl acrylate
TPO: 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide
DETX: 2, 4-diethylthioxanthone
UV 5: light stabilizers
UV 22: light stabilizers
BYK-315N: polyester-modified polymethylalkylsiloxane surfactant, solid content 25 mass%, solvent component: mixture of Methoxypropyl Acetate and phenoxyethanol with mass ratio of 1/1
[ aluminum adherence ]
Ink jet printing was performed on an aluminum film using each of the photocurable ink compositions for ink jet printing obtained in examples 1 to 5 and comparative examples 1 to 4.
The adhesion of the obtained printed portion was confirmed by the following method.
After a transparent tape (cellophane tape) made of nicoiban was attached, the degree of peeling of the surface of the ink cured film when the transparent tape was peeled off was visually evaluated.
○ No peeling
X: at least a part of the coating film is peeled off
[ Heat resistance of coating film ]
Ink jet printing was performed on an aluminum film using each of the photocurable ink compositions for ink jet printing obtained in examples 1 to 5 and comparative examples 1 to 4.
The obtained aluminum film with a coating was stored at 60 ℃ for 1 day, and the state of the coating was observed.
○ the coating film was adhered to the surface of the aluminum film just after printing
X: the coating film is peeled off from the surface of the aluminum film or easily peeled off when touched by fingers
[ Table 1]
Figure BDA0002364121550000111
From the results shown in table 1, it is understood that the ink compositions of the present invention have excellent adhesion to aluminum and good heat resistance of the coating film, according to examples 1 to 5, which are the photocurable ink compositions for inkjet printing of the present invention. However, according to comparative example 1 which does not contain a monofunctional monomer having a Tg of 100 ℃ or higher and comparative example 3 which does not contain an amine-modified acrylic oligomer in a proportion of 80 mass% or higher of the monofunctional monomer relative to all the monomers, a result that the heat resistance of the coating film is poor was obtained. Further, according to comparative example 2 containing an excess amount of monofunctional monomer having Tg of 100 ℃ or higher and comparative example 4 containing no acid-modified acrylic monomer, a result of poor adhesion to an aluminum film was obtained.
As a result, the photocurable inkjet printing ink composition of the present invention having a specific composition can exhibit the effect of sufficient adhesion to the surface of aluminum or the like and the effect of excellent heat resistance of the coating film in a well-balanced manner.

Claims (2)

1. A photocurable ink composition for inkjet printing, characterized in that, with respect to the entire ink composition,
containing an acid-modified acrylic monomer in an amount of 0.1% by mass or more,
10 to 30 mass% of a monofunctional monomer having a Tg, i.e., a glass transition temperature of 100 ℃ or higher,
with respect to all of the monomers, the monomer,
the monomer contains a monofunctional monomer in an amount of 80% by mass or more.
2. The photocurable inkjet printing ink composition according to claim 1, wherein the monofunctional monomer having a Tg of 100 ℃ or higher is a monofunctional monomer having a Tg of 120 ℃ or higher.
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